Dialkylphosphitoalkyl acrylates and methacrylates and process for preparing same



DIALKYLPHOSPHITOALKYL ACRYLATES AND METHACRYLATES AND PROCESS FOR PRE-PARING SAME Constance A. Lane, Philadelphia, Pa., assignor to Rohm 8:Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing.Application December 11, 1957 Serial No. 701,960

9 Claims. (Cl. 260 -461) The present invention relates to polymerizablephosphorous ester derivatives of hydroxyalkyl esters of ,5-ethylenically unsaturated monocarboxylic acids, and more particularly todialkylphosphitoalkyl acrylatcs and methacrylates, and to a process forpreparing same, as well as polymers and copolymers containing suchesters. The novel polymerizable esters of this invention comprise a newclass of compounds, which contain as distinct and separate groups withintheir structure both an ester group derived from an a,[3-ethy1enicallyunsaturated monocarboxylic acid and an ester group derived fromphosphorous saturated aliphatic hydrocarbon group.

These new compounds have the general formula:

is a straight-chain, branchedor cyclic alkylene group having two to sixcarbon atoms, and R and R each represent an alkyl group having one tofour carbon atoms, or when taken together represent an alkylene grouphaving two to six carbon atoms. Typical compounds within the scope ofthis invention are the following:

vOCJHs CHFCH-CO CHzCHgOP Dlmethylphosphitoethyl acrylate OCaHiCHr-CHCO:CH:CH:OP

' Cz n Dlethylphosphitoethyl acrylate om=on-oo,cmomor OCIHBDibutylphosphitoethyl acrylate OCH:

CHI=C COL CHQCHQOP H: OCH; Dimethylphosphitoethyl methacrylate V, OCIH'cm=o-co,on,on,or

V H: 00211: Diethylphosphitoethyl methacrylate OCH(CH;)',

orr o-o OZQHICHIOP V H: OCH(OH;) D1isopropylphosphltoethyl methacrylate-2,934,554 Patented Apr. 26, 1960 OCH:

CHz=(iJ-C 0301120110 P CH, CH; 0011,

6 2-d'imethylphosphltopropyl methacrylate CH: CH! 001E;

1 2-diethylphosphitopropy1 methacrylate -2-diethylphosphito1-buty1methacrylate 001E;

011,:0-0 owmomomonzor CH5 0 C 2 5 4-diethylphosphitobuty1 methacrylate25 O-CH: acid, these groups being attached to the same divalent oHi=oH-C memento 1/ O-GH:

Ethylenephosphitoethyl acrylate OCH: oni cfcoaon onlor I on, V O-on,Ethylenephosphitoethyl methacrylate CH3 'CH3 OCH1 capo-commoner V 0-011,Ethylenephosphitopropyl methacrylate O-CH: CHFJJ-COrCHzCHiO P O-CH'CHI1,2-propylenephosphitoethy1 methac'rylate CH3=CC O2CH1CH2CH2CH2CH2OP H:f r CzHs 5-dlethylphosphitopenty1 methacrylate CH:=CCOiUHaCHaCHnCHgCHzCHaOP Ha O C 1H5 G-diethylphosphitohexyl methacrylate 7*f -dirnethylphosphitocyclohexyl acrylate acting, under controlledtemperature conditions, an hydroxyalkyl ester of an u,B-ethy1enica11yunsaturated mono- 1:08.1'bOXY1iC acid with an. appropriate derivativeof'phos- 0 phorous acid, such as a tertiary'esterlof phosphorous acid,i;e.,- a trialkyl phosphite; or a dialkylnhalophosphite. Of

such derivatives of phosphorous acid, the dialkyl-chloro- 'Ihecompoundsof this invention are prepared by rephosphites are preferred startingmaterials for this reaction, which is best carried out in the presenceof a hydrogen halide acceptor such as pyridine, triethylarnine,dimethylaniline or the like. An inert solvent such as benzene, toluene,chloroform or the like may also be employed to advantage to assist inbringing about the reaction.

The hydroxyalkyl esters of a,fi-ethylenically unsaturated monocarboxylicacids used as starting materials in accordance herewith are exemplifiedby 2-hydroxyethyl acrylate, methacrylate, Z-hydroxypropyl methacrylate,4- hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate,6-hydroxyhexyl methacrylate, 2, 3-, or 4-hydroxycyclohexyl methacrylate,and the like.

Trialkyl phosphites which are suitable as starting materials in thepractice of this invention include trimethyl phosphite, triethylphosphite, and the like.

Dialkyl chlorophosphites which may be used as starting materials includedimethyl, diethyl, diisoprop-yl, ethylene, propylene chlorophosphites,and the like.

The hydroxyalkyl esters of a,,8-ethylenically unsaturated monocarboxylicacids which are used as starting materials in accordance with thisinvention are prepared according to published procedures, e.g., byreaction of the fl-ethylenically unsaturated monocarboxylic acids withethylene or propylene oxidesee, for instance, United States Patent No.2,484,487or by direct esterification of these acids with the appropriateglycol-see for instance, British Patent No. 595,881-or by reaction ofthe acid chlorides with the appropriate glycol-see, for instance, UnitedStates Patent No. 2,335,813 and Burtle, Saam and Mokrasch, J. Org. Chem.17, 1302 (1952)- or by the reaction of the alkali metal salts of theseacids with ethylene or propylene chlorohydrin-see, for instance, UnitedStates Patent No. 2,129,722or by other miscellaneous methodssee, forinstance, United States Patent No. 2,338,967 and United Statesapplication Serial No. 623,302, filed November 20, 1956.

The phosphorous-containing reagents which are used as starting materialsin accordance with this invention are either commercially available ormay be prepared from readily available intermediates according topublished procedures-see, for instance, Cook, Ilett, Saunders, Stacey,Watson, Wilding and Woodcock, J. Chem. Soc. 1949, 2921, and Lucas,Mitchell and Scully, J. Amer. Chem. Soc. 72, 5491 (1950).

The following examples further illustrate specific embodiments of thisinvention.

EXAMPLE 1 Preparation of Z-aiethylphosphitdethyl methacrylate ing to 150C. for four hours a total of 39 ml. of distillate was collected.Distillation of the residue under high vacuum gave 55 grams (32% yield)of 2-diethylphosphitoethyl methacrylate, B.P. 90120/0.02 mm., n 1.4418,10.6% P (theo. 12.4% sap. No. 450 (theo. 450). Upon redistillation themonomer distilled at 80-93/ 0.1 mntu; 12 1.4405, 11.3% P.

EXAMPLE 2 Preparation of 2-diethylphosphitopropyl methacrylate Reactionof 72 grams (0.5 mole) of Z-hydroxypropyl methacrylate and 83 grams (0.5mole) of triethyl phosphite under conditions similar to those in Example1 gave a 48% yield of 2-dicthylphosphitopropyl methacrylate, B.P. 12014SC./0.2 mm., n 1.4381, 10.7% P (theo. 11.8% P).

4 EXAMPLE 3 Preparation of ethylenephosphitopropyl methacrylate In a oneliter 3-neck flask, equipped with a stirrer, thermometer, additionfunnel, condenser and drying tube, Were placed 72 grams (0.5 mole) of2-hydroxypropyl methacrylate, 43.5 grams (0.55 mole) of pyridine, 500ml. of anhydrous ether, and 1.0 gram of N.N-di-2(1.4- naphthoquinonyl)-p-phenylenediamine. The reaction mixture was cooled to 510 C. and 63grams (0.5 mole) of ethylene chlorophosphite (Lucas, Mitchell, Scully,J. Amer. Chem. Soc. 72, 5489 (1950)) was added over a period of thirtyminutes. After filtration of the pyridinehydrochloride and addition of1.0 gram of N,Ndi-2(1,4- naphthoquinonyl)-pphenylenediamine, the etherwas removed under reduced pressure. Distillation gave 59 grams (51%yield) of ethylencphosphitopropyl methacrylate, B.P. 73-80 C./0.02 mm.,11 1.4635, sap. No. 524 (theo. 480), 12.6% P (theo. 13.3% P).

EXAMPLE 3a 2-ethylenephosphitoetlzyl acrylate In a 200 ml. 3-neck flask,equipped with a stirrer, thermometer, addition funnel and a condenserfitted'with a drying tube, were placed 11.6 grams (0.10 mole) of2-hydroxyethyl acrylate, 8.7 grams (0.11 mole) of pyridine, 100 ml. ofanhydrous ether, and 0.2 gram of hydroquinone. The reaction mixture wascooled to 05 C. and 12.6 grams (0.10 mole) of ethylene chlorophosphite(Lucas, Mitchell and Scully, J. Amer. Chem. Soc. 72, 5489 (1950)) wasadded over a period of one hour. The precipitated pyridine hydrochlorideWas removed by filtration and the ether removed under reduced pressure.The residue was a clear, yellow oil which amounted to 18.6 grams yield)and was identified as 2-ethylenephosphitoethyl acrylate.

EXAMPLE 4 Preparation of ethylencphosphitocthyl methacrylate In a mannersimilar to that described in Example 3, ethylenephosphitoethylmethacrylate, B.P. 75-80 C./0.02 mm., was obtained in 39% yield.

EXAMPLE 5 Preparation of polymeric compositions plastics, coatings,textile finishes, etc.

I claim: 1. A compound having the general formula CHz=oi 0AoP it v o R,

wherein R is a member of the class consisting of hydrogen and methyl, Rand R each is a member of the class consisting of alkyl groups of notover four carbon atoms and when taken together represent an alkylenegroup having two to six carbon atoms, and A is a member of the classconsisting of alkylene groups having two to six carbon atoms.

2. Diethylphosphitoethyl methacrylate.

3. Diethylphosphitopropyl methacrylate.

4. Ethylenephosphitoethyl methacrylate;

5. Ethylenephosphitopropyl methacrylate. 6. 1,Z-propylenephosphitoethylmethacrylate. 7. A process for preparing a compound of the formula and acompound of the formula 7 OR: 1 wherein R, A, R; and R, have the abovemeanings, and

wherein R, is an alkyl group of not over four carbon atoms.

6 8. A process for preparing diethylphosphitoethyl methacrylate whichcomprises reacting triethyl phosphite with Z-hydroXyethyl methacrylateby heating together in the presence of a free-radical polymerizationinhibitor.

9. A process for preparing diethylphosphitopropyl methacrylate whichcomprises reacting triethyl phosphite with 2-hydroxypropyl methacrylateby heating together in the presence of a free-radical polymerizationinhibitor.

References Cited in the file of this patent UNITED STATES PATENTS2,325,076 Renter July 27, 1943 2,326,140 Gzemski Aug. 10, 1943 2,349,462Reuter May 23, 1944 2,353,558 Gzemski July 11, 1944 2,636,027 Coover etal. Apr. 21, 1953 2,666,778 Steinberg Jan. 19, 1954 2,743,261 Coover eta1. Apr. 24, 1956 2,765,331 Whetstone et a1. -3. Oct. 2, 1956 OTHERREFERENCES Lucas et al.: I. Am. Chem. Soc.," 72, 5491-7 (1950).

Hoffman et al.: J. Am. Chem. Soc., 78, 5817-5821

1. A COMPOUND HAVING THE GENERAL FORMULA
 7. A PROCESS FOR PREPARING ACOMPOUND OF THE FORMULA